Method for the preparation of 1-chloro-3-bromo-2-(2-chloroethoxy)-propane and the compound prepared



Patented Mar. 16, 1948 METHOD FOR THE PREPARATION OF 1- CHLORO 3 BROMO 2 (2-CHLOR0- ETHOXY)-PROPANE AND THE COM- POUND PREPARED Robert M. Vance, Cleveland, Ohio, and Amos G. Horney, Plattsburg, N. Y., assignors to Air Reduction Company, Incorporated, New York, N. Y., a corporation of Delaware No Drawing. Application August 14, 1947, Serial No. 768,702

7 Claims. (Cl. 260-614) pure compound.

Other objects and advantages of the invention will be apparent as it is better understood by reference to the following specification, in which the preferred embodiments of the invention are described.

The new compound 1-chloro-3-brom0-2- (2-chloroethoxy) -propane has the structural formula CHzBr-CH-CHzCl It is a colorless liquid with a characteristic ethereal odor, and has a boiling point of 81-815 at 1 mm. Other characteristics are D 1.577 and n g= 1.5033

Preparation of the new compound is best effected by reaction of allyl bromide with ethylene chlorohydrin and chlorine. It is necessary first to prepare allyl bromide by the reaction: om=cn-orn-0H NzBr mso. H2O

CHFCHrCHzBr The reaction may be carried out in a five-liter flask fitted with a stirrer, downward condenser and addition funnel. 1350 cc. of water are placed in the flask and 1545 grams (15 mols) of sodium romide are introduced with stirring. Then 699 grams (l2 mols) of allyl alcohol are added, and finally 2000 grams (1087 cc.) of sulfuric acid are fed gradually to the mixture. The flask is then heated and the product distilled with steam. After separation, the product is washed with a dilute aqueous solution of sodium carbonate, dried over calcium chloride and redistilled. The distillate to 70 is allyl bromide suitable for use in the preparation of the new compound. Allyl bromide prepared by any other method may be used.

The new product which is the subject of the present invention is prepared by the reaction: oH,=oH-oH.-Br onion-cruel on CHzBr-OH-CHzOl In this reaction 966 grams (12 mols) of ethylene chlorohydrin is placed in a. two-liter, threeneck flask, fitted with an'addition funnel, addition tube, stirrer, thermometer and HCl exit tube and cooled to 0 C. 940 grams (7.8 mols) of allyl bromide and chlorine, less than the stoichiometric equivalent of the ethylene chlorohydrin, as required are added simultaneously at such a rate that the mixture remains just on the green side while the temperature is held at about 0 C. Upon completion of the reaction, air is introduced to expel the hydrochloric acid and the balance of the latter is removed with heat and vacuum. The product is distilled under reduced pressure to separate the desired product. The yield based on allyl bromide was 29%. Based on ethylene chlorohydrin used the yield was 77 As a further illustration of the present invention, 18 mols of allyl bromide and 18 mols of chlorine were gradually added with stirring to 37.5 moles of ethylene chlorohydrin while the reaction mixture was maintained at a temperature of minus 10 to 0 C. The reaction was effected in such a manner that a faint green color was present in the reaction mixture during the addition of the allyl bromide and chlorine. After the completion of the addition of the allyl bromide and chlorine, the reaction mixture was permitted to warm to room temperature, and the hydrogen chloride was removed at reduced pressure, using a water bath. The reaction mixture was then vacuum distilled to yield 6.34 mols (a 35.2% yield, based upon the amount of allyl bromide employed as a reactant) of l-chloro- 3-bromo-2-(2-chloroethoxy) -propane, together with recovered ethylene chlorohydrin and. products other than that desired.

As a still further illustration of the method for the preparation of the compound of the present invention, an experiment similar to that described in the previous paragraph was run, except that 2 mols of allyl bromide, 2 mols of chlorine, and 4 mols of ethylene chlorohydrin were employed as reactants and that the reaction was fected at temperatures within the range 45-50 C. This experiment yielded 0.655 mol of l-chloro- 3-bromo-2-(2-chloroethoxy)-propane, a 32.8% yield, based upon the amount of allyl bromide employed as a reactant.

Various modifications may be made in the foregoing teachings to result in the production in good yield of the desired product. Thus, the temperature at which the reaction between the allyl bromide and the ethylene chlorohydrin and chlorine takes place does not appear to be criti- 3 cal, since satisfactory yields of the desired product may be obtained at temperatures as low as minus lOF C. and as high as' '50*CL,'as the;fore going teachings illustrate. Furthermore, thereaction may be effected at even lower or higher temperatures to produce the desired product in ood yield. Likewise, the reaction may be ref-- fected at atmospheric, sub-atmospheric, or super atmospheric pressures. Fonreasonsof convenience,'however, it is preferred that the reaction be effected at a temperature within the range from about minus 15 C. to"aboutfplus 75 C;

and at a pressure which issubstantiaIIytatmoB- pheric.

The procedure as described afiords a satisfactory and practicable procedure 'for'thepreparw tion of the desired product which may be carried out with suitable modification of theapparatus used to prepare the product for commercial use.

This application is a continuation-impart of our application Serial 'No.540,'318, filed June 14, 1944, entitled 1.-ch1oro-3-bromo.-2-(2 -'ch1oroetho y) Dropane'and'method of preparing it.

We claim:

'1. A new chemical compound, I-chloro-3- bromo-2-(2-chloroethoxy) -jpropane, with the structural formula:

2. The method of preparin 1-chloro-'3-bromo- 2- (2-chloroethoxy) -propane which comprisesreacting allyl'bromide with ethylene ..chiorohydrin and chlorine.

'3. The method otpreparing,l chloro-3ebromo- 2- (2-chloroethoxy) -propane which comprises'reacting allyl'bromide with ethylene chlorohydrin and chlorine-at a temperature within the range of from about minus 15 C. to about plus 75 C.

4. The method of preparing 1-chloro-3-bromo- 2-(2-chloroethoxy) -propane which comprises reactingallyl *bromide with'f'ethylene. chlorohydrin -and"chlorineat 'a temperature'within-the' range of from about minus 15 C. to about plus C. and at a pressure which is substantially atmospheric.

5. The method of preparing 1-chloro-3-bromo- ;2 (2echloroethoxy) -propane which comprises react-ing :allylbromide with ethylene chlorohydrin 'and chlorine, r the ethylene chlorohydrin being in excess of.the stoichiometric equivalent of the allyl bromide, .an'dithe chlorine being added to the rea'ctiomatsucharate and in such amount as to '2- (Z-chloroethoxy) apropane which comprises .re-

acting, at a temperature within therangefrom about minus 15 'C..to about plusf75 'C'. and at a pressure whichis substantially atmospheric, allyl bromide with ethylene chlorohydrinand chlorine, the ethylene chlorohydrin being inexcessofj the stoichiometric equivalent. of the. allylbromide and the chlorine being:addedto'thereaction at such a rate and'in such amountas. to maintain agreen color in the reacting solution.

ROBERT- M. VANCE. AMOS G. HORNEY. 

